Process for producing indoanilines and keratin fiber dye composition containing the same

ABSTRACT

A two-stage process for producing indoanilines includes oxidizing in a first stage a paraphenylene diamine to a quinone diimine and in a second stage condensing the said quinone diimine with a phenolic compound. The resulting indoanilines can be incorporated into a dye composition for keratinous fibers, especially, human hair.

United States Patent Kalopissis et a1.

PROCESS FOR PRODUCING INDOANILINES AND KERATIN FIBER DYE COMPOSITION CONTAINING THE SAME Inventors: Gregoire Kalopissis, Paris; Andree Bugaut, Boulogne-sur-Seine; Francoise Estradier, Paris, all of France Assignee: Societe Anonyme dite: LOreal,

Paris, France,

Filed: Feb. 28, 1973 Appl. No.: 336,802

Related U.S. Application Data Continuation-impart of Ser. No. 97,395, Dec. 11, 1970, abandoned, which is a continuation-in-part of Ser. No. 45,564, June 11, 1970, abandoned.

Foreign Application Priority Data June 11, I969 Luxemburg............................ 58848 U.S. CI. 8/l0.l; 3/10; 8/10.2; 8/11; 260/396 N; 260/562 R; 260/570 SC; 260/570.7; 260/577; 260/578; 424/D1G. 1;

424/DIG. 2; 424/47; 424/70 Int. CI. A6IK 7/12;A61K 7/13; A61K 7/I35;D06P 1/32 Field 01' Search 8/10, 11, 10.2, 10.1;

260/396 N, 575, 562 R, 570 SC, 570.7, 578, 577

[56] References Cited UNITED STATES PATENTS 3,210,252 10/1965 Blanke et al 8/1 1 3,591,323 7/1971 Kalopissis et al. 8]]! 3,712,790 1/1973 Kalopissis et al. 8/1 I 3,787,174 1/1974 Kalopissis et a1. 8/11 3,811,831 5/1974 Bugaut et al 8/11 FOREIGN PATENTS OR APPLICATIONS 436,574 11/1967 Switzerland 8/10.2 625,997 12/1962 Belgium 8/11 27,000 8/1906 United Kingdom 260/396 N 7,838 4/1906 United Kingdom 260/396 N 12,644 8/1915 United Kingdom 8/11 Primary Examiner-Benjamin R. Padgett Assistant ExaminerT. S. Gron Attorney, Agent, or Firm-Cushman, Darby & Cushman [57] ABSTRACT A two-stage process for producing indoanilines includes oxidizing in a first stage a paraphenylene diamine to a quinone diimine and in a second stage condensing the said quinone diimine with a phenolic compound. The resulting indoanilines can be incorporated into a dye composition for keratinous fibers, especially, human hair.

9 Claims, No Drawings PROCESS FOR PRODUCING INDOANILINES AND KERATIN FIBER DYE COMPOSITION CONTAINING THE SAME wherein R and R each independently represent a member selected from the group consisting of hydrogen, halogen, lower alkyl, lower alkoxy, a ureido radical and -NHCOR group wherein R is lower alkyl;

R represents a member selected from the group consisting of hydrogen, halogen, lower alkyl, lower alkoxy, a ureido radical, -NHCOR wherein R is lower alkyl and -NHR wherein R, represents a member selected from the group consisting of hydrogen, lower alkyl, hydroxy lower alkyl and carbamylmethyl with the proviso that when R is -NHR,,, R is not hydrogen;

R R R and R, each independently represent a member selected from the group consisting of hydrogen, halogen lower alkyl and lower alkoxy radical, it being understood that the terms lower alkyl or alkoxy mean those having I to 4 carbon atoms and that the above formula does not exclude the tautomeric forms of these compounds.

The dye compositions of the invention can be aqueous solutions, including aqueous solutions of a lower alkanol. Additionally, the aqueous solutions can include a cosmetic resin, especially when a colored hair set lotion is contemplated.

The dye composition of the present invention contains from about 0.02 to 0.3 percent by weight, preferably, between about 0.05 to 0.2 percent by weight of said indoaniline.

The indoaniline as defined above can be used alone, in which case tints varying from purple to blue-green are obtained or in admixture with other capillary dyes such as azo or anthraquinone dyes.

The pH of the dye composition of the present invention can vary within wide limits, and generally the pH will range between 5 and l l, and preferably between 7 and ll.

As stated above the dye composition of this invention can be in the form of aqueous solution including an aqueous lower alkanol solution, but it can also contain conventionally employed cosmetic thickeners and thus take the form of creams or gels.

The dye composition of the present invention can additionally include various ingredients that are customarily used in cosmetics, such as wetting agents, dispersants, swelling agents, penetrating agents, emol- 2 lients or perfumes and it can also be packaged in aerosol cans using conventional propellants such as the chlorofluorohydrocarbons.

The dye composition of the present invention is readily prepared by dissolving in water or in a mixture of water and a lower alkanol such as ethanol and isopropanol, one or more indoanilines as defined above, alone, or in admixture with another dye.

The dyeing of keratinic fibers, particularly human hair, by means of the dye composition of the invention can be effected in the usual way by applying the composition on the fibers that are to be dyed, permitting it to remain in contact with the fibers for about 5 to 30 minutes, rinsing the fibers and, if desired, washing the fibers, followed by drying the thus dyed fibers.

When the dye composition of the present invention is to be included in a hair set lotion, conventional cosmetic film-forming resins can usefully be employed therewith. These conventional resins include polyvinylpyrrolidone, copolymers of polyvinylpyrrolidone and vinyl acetate, copolymers of vinyl acetate and an unsaturated carboxylic acid such as crotonic acid, copolymers resulting from the copolymerization of vinyl acetate, crotonic acid and an acrylic or methylacrylic ester, copolymers resulting from the copolymerization of vinyl acetate and a vinyl alkyl ether, copolymers resulting from the copolymerization of vinyl acetate, crotonic acid and a vinyl ester of a long carbon chain acid or an allyl or methallyl ester of a long carbon chain acid, copolymers resulting from the copolymerization of an ester formed from an unsaturated alcohol and a short carbon chain acid, an unsaturated short carbon chain acid and at least one ester formed from a saturated alcohol and an unsaturated short carbon chain acid, and copolymers resulting from the copolymerization of at least one unsaturated ester and at least one unsaturated acid;

Representative specific cosmetic film-forming resins include polyvinylpyrrolidone having a molecular weight ranging from about 10,000 to 700,000 copolymers of vinylpyrrolidone and vinyl acetate wherein the ratio of PVP to PVA ranges between 30:70-70:30, copolymers of maleic anhydride and butyl vinyl ether, copolymers of vinyl acetate and allyl stearate and allyloxy acetic acid, copolymer of methyl methacrylate and stearyl methacrylate and dimethyl methacrylate, and the like. These resins are utilized in a proportion of about 1 to 3 percent by weight of the total composition.

The alcohols suitable for preparation of such hair set lotions are lower alkanols, preferably ethanol and isopropanol, which are present in amounts of about 20 to 50 percent by weight of the total hair set lotion composition. These lotions are utilized in the customary way by applying the same to set hair which has been washed and rinsed, followed by rolling up and drying of the hair.

Among the indoanilines having the formula set forth above, those in which at least two of the radicals R, to R, are not hydrogen atoms and in which R, and R are not both chlorine atoms are new compounds and thus these new compounds are also an embodiment of the present invention.

The indoanilines, useful in the dye compositions of this invention, including the novel indoanilines of this invention can be prepared according to two different processes, one of which is a further embodiment of the present invention, the other having already been known in the art.

wherein R R, and R, also have the meanings given above. The condensation reaction is effected in an aqueous medium with a pH ranging from about 8 to l l, in the presence of an oxidizing agent and at a temperature between 0 and 40C.

The oxidizing agent used in this condensation reaction can be, for example, hydrogen peroxide, potassium persulfate, potassium ferricyanide or sodium hypochlorite and is present, generally in amounts ranging from about 10 to 70 weight percent of the total weight of the paraphenylene diamine and phenol reactants.

Representative phenols that can be used to prepare the compounds of the inventioninclude phenol, 2,6- xylenol, 2,5-xylenol, S-amino-Z-methyl phenol, 5- amino-2-chloro phenol, N-S-methylamino-Z-methyl phenol, N-5-earbamylmethylamino-Z-methyl phenol, 2,6-dimethyl-3-amino phenol, N-3-acetylaminophenol, N-S-acetylamino-Z-methyl phenol, N-Z-acetylamino phenol and N-3-acetylamino-2,G-dimethylphenol.

Suitable paraphenylene diamines which can be used in preparation of the indoanilines of the invention are, for example, paraphenylene diamine, paratoluene diamine, 2,5-diamino anisole, 2,5-diamino chlorobenzene, 2-methoxy-5-methyl-paraphenylene diamine, 2,6-dimethyl-3-methoxyparaphenylene diamine and l ,4-diaminodurene.

The mole ratio of paraphenylene diamine to phenol can range between about 3/] to 1/1 and is preferably 1/].

The indoanilines of this invention in which at least two of the R R R, and R radicals are not hydrogen atoms can also be prepared according to a novel process of this invention. This novel process comprises oxidizing a paraphenylene diamine as defined above to a quinone diimine in a first stage, the formula of the said quinone diimine being:

wherein R R R, and R have the above meanings, and condensing in a second stage the resulting quinone diimine on a phenol compound also as defined above.

Oxidation of the starting paraphenylene diamine to quinone diimine is effected by heating the paraphenylene diamine to a temperature between 30 and C. in an anhydrous solvent such as ethyl ether or isopropyl ether in the presence of a mild oxidizing agent such as silver oxide or lead oxide. The amount of oxidizing agent will range between about [,5 to 2 mole for 1 mole of the paraphenylene diamine, and is preferably [,5 mole for 1 mole of this compound.

The resulting quinone diimine is separated from the reaction mass by any convenient separation technique such as by filtration, followed by evaporation of the filtrate to dryness with purification by recrystallization in an anhydrous solvent before being condensed on the phenol compound, the condensation reaction being effected at a temperature ranging from about ambient temperature to about 40C. either in an aqueous me dium, preferably one containing ammonia in amounts of about 2 to 4 weight percent of the total aqueous medium, or in an inert solvent, e.g. ether or benzene. Generally, the mole ratio of quinone diimine to phenol is ll 1.

The quinone diimines prepared in the first stage of this new process of the invention are, with the exception of duroquinone diimine, new compounds.

The following examples are intended to illustrate the different aspects of the present invention. The temperature indicated in these examples are in Celsius and, unless otherwise specified, all parts and percentages are by weight.

EXAMPLE I N-[(4'-amino-3',5-dimethyl-2'-methoxy)phenyl] benzoquinone imine is prepared in accordance with the following reaction:

OCH

0.025 moles (6g) 2,6-dimethyl-3-methoxy-paraphenylene diamine dichlorhydrate are dissolved in 250 cc water to which 12.5 cc ammonia of 22 Be strength has been added. The solution thus obtained is added to 0.025 moles (2.35 g) phenol previously dissolved in 250 cc water to which cc ammonia of 22 Be strength has been added. There is then added to this mixture, with vigorous agitation, 0.05 moles (16.45 g) of potassium ferricyanide in solution in 300 cc water. After having allowed the mixture to stand for one hour at l0 it is then filtered on a suction filter and washed with water, the said resulting product being the above identified indoaniline in a yield of 2.3 g which, after 5 recrystallization in an acetone-water mixture, melts at mine dichlorhydrate in 600 cc of a 0.2 N NaOH solu- 127. tion. A second solution is prepared by dissolving 0.06 mole (7.32 g) 2,5-xylenol in 600cc of a 0.2 N NaOH solution. These two solutions are mixed and there is Analysis f rgfgf' Found 5 then slowly added thereto, with agitation, a solution of 0.06 mole (16.20 g) potassium persulfate in 600 cc g3: 23; 2;; g 34 water. When the addition is completed, the resulting mixture is allowed to stand for one hour at ambient EXAMPLE 2 temperature and then the 9.1 g indoaniline is separated by filtering the reaction mass on a suction filter. After recrystallization in a dimethyl formamide and water mixture, the said indoaniline exhibited a melting point N-[(4'-amino-3',5' dimethyl 2'-methoxy)phenyl] 2,6-dimethyl benzoquinone imine is prepared in accordance with the following reaction: of

0H CH 3 3 3 3 H N NH OH N N S 0 2 OCH CH OCH 3 3 CH 3 CH A first solution is prepared by dissolving 0.05 moles Calculated for (14.34 g) 2,6-dimethyl-3-methoxy paraphenylene di- Analysis C H,,N,O, Found amine dichlorhydrate in 500 cc of a 0.2 N NaOH solu- C 7133 72m tion. A second solution is prepared by dissolving 0.05 H 7.04 7.04 moles 7.32 g) 2,6-xylenol in 500 cc of a 0.2 N NaOH N solution. The two solutions are then mixed and to the EXAMPLE 4 resulting mixture there is slowly added, with agitation, 0.05 mole (13.50 g) potassium persulfate dissolved in 500 cc water. when the addition is finished, the reaction mixture is allowed to stand for 1 hour at 0. The

N-[(4'-amino)phenyl] 5-amino-2-methyl benzoquinone imine is prepared in accordance with the follow ing reaction:

N112 above-identified indoaniline is then recovered by filtering reaction mass on a suction yield To a solution of0.03 mole (5.44 g) paraphenylenediamoummg to After F 'Y fF m an amine dichlorhydrate dissolved in 100 cc water, ammotone-water mixture, the said mdoamlme recovered nia is added in amounts Sufficiem to adjust the PH melts at 123 thereof to 8. This solution is immediately added to a solution of 0.01 mole (1.23 g) S-amino Z-methyl phe- Calculated for Analysis c ll mo, Found no] in 100 cc water. 30 cc ammonia 22 Be and 150 cc C 72.04 hydrogenperoxide to rnake 20 volumes are then added H 7.04 6.99 to this mixture which 18 then allowed to stand for 10 N hours at room temperature. 2 g of the said indoaniline in crystalline form is recovered by filtering the reaction EXAMPLE 3 mass on a suction filter. After washing with water and N-[(4'- i 3',5' 2' methoxymhenyll acetone and recrystallizing the same from a dimethyl- 2,5 di h benzoquinone i i i prepared i accorformamide and water mixture, the resulting indoaniline dance with the following reaction: had a melting paint of 236.

CH C11 CH CH H N Ill-l OH H N N 0 0011 CH OCH CH 3 CH Calculated for Analysis C|,H,;N,O Found I C 68.72 68.65 68.51 A first solution 18 prepared by dlSSOlVll'lg 0.06 mole H 5.72 5.93 5 74 (14.34 g) 2,6-dimethyl 3-methoxy-paraphenylenedia- 13-50 1819 13:25

7 8 EXAMPLE thus obtained there is introduced, little by little, with agitation, 0.025 mole (8.22 g) potassium ferricyanide g u n 3 amino 6 methy] in solution in 150 cc water. 1.8 g crystalline indoaniline benzoquinone imine is prepared in accordance with the 5 as defined recovered y i g the reactlfm following reaction; mass on a suction fllter. After washlng the same with 0.025 mole (4.87 g) paratoluylenediamine dichlorhywater and after recrystallizing the said indoaniline from drate is dissolved in 200 cc water and is made alkaline a mixture of dimethylformamide and water, the said with sufficient ammonia to bring the pH thereof to 8. indoaniline. melting at Obtaincd- This solution is immediately added to a solution of 0.02 mole (2.46 g) S-amino 2-methyl phenol in 200 cc water to which 60 cc ammonia 22Be is added. To the result- Calculated mg mixture thus obtained there is added, little by little, nalysls Found in the course of 20 minutes with agitation, 0.05 mole 2-3; g-3g 2%; (16.45 g) potassium ferricyanide dissolved in 250 cc N :3 15:84 15:80 water. 25

1.5 g of the above indoaniline is recovered by filtering the reaction mass on a suction filter and it is then EXAMPLE 7 washed with water. After recrystallization in a pyridine N-[(4'-amino 3'-chloro) phenyl] 3-amino 6-methyl and water mixture, the said indoaniline, melting at benzoquinone imine is prepared in accordance with the 130, is recovered. following reaction:

CH3 CH3 H N NH 0H H N N Fe CN K 3 c1 NR 2 Calculated for 0.02 mole (2.46 g) S-ammo 2-methyl phenol and Analysis CIHSNO Found 0.02 mole (2.85 g) chloroparaphenylene dlamlne are dissolved in 200 cc water to which has been added 68.24 68.40 5?; 2;; 517 13 cc ammonia 22Be'. To this mixture there is added, N 17-42 17-03 l7-0l 43 little by little with agitation, 0.04 mole 13.16 g) potassium ferricyanide. The reaction mass is then filtered on EXAMPLE 6 a suction filter and a yield of 5 g of said indoaniline is obtained. After recrystallization in'a pyridine and water I N [4 ammo 2 methoxwphenylp ammo 6 methy mixture, the said indoaniline recovered melts at 120.

benzoquinone imine is prepared in accordance with the 50 following reaction:

CH CH H N NH OH H N N:

2 2 Fe(CN) K 2 0on NH 0on KH 0.125 mole (2.63 g) 2,5-diamino anisole dichlorhydrate is dissolved in 100 cc water, and the resulting solution is made alkaline by addition of Sec ammonia alcu a d for 22Be. This alkaline solution is then added to 0.0125 CMHI'MCO Found mole (1.54 g) S-amino Z-methyl phenol previously C% 59.66 52.33 dissolved in cc water, to which there has been 5% 2:32 15-66 1530 added 45 cc ammonia 22Be'. To the resulting mixture 9 EXAMPLE 8 N-[4'-amino 3',5'-dimethyl 2' methoxy) phenyl] 3-amino 6methyl benzoquinone imine is prepared in accordance with the following reaction:

10 the reaction mass on a suction filter. After recrystallization in a pyridine and water mixture, the recovered product exhibits a melting point of 222.

CH3 CH3 CH3 CH3 H N H) N N o CH NH OCH NH CH3 3 2 CH3 3 2 0.0113 mole (2.7 g) 2,6dimethyl 3-meth0xy paraphenylene diamine is dissolved in 75 cc water to which 3 cc ammonia 2286 has been added. This solution is then immediately added to 0.0075 mole (0.92 g) 5amino 2-methyl phenol previously dissolved in 75 cc water. 22 cc ammonia 22Be' and 100 cc hydrogen peroxide to make 20 volumes are added to this mixture which is then allowed to stand at room temperature for 15 hours. 0.95 g of the above indoaniline is then recovered by filtering the reaction mixture on a suction filter 25 the said recovered indoaniline melting at 205 after recrystallization in a mixture of pyridine and water.

N-[(4'-amino tetramethyl) phenyl] S-amino 2- methyl benzoquinone imine is prepared in accordance with the following reaction:

Calculated for Analysis C H N O Found EXAMPLE 10 N-[(4-amino 3-chloro)phenyl] 3-amino 6-chlor0 benzoquinone imine is prepared in accordance with the following reaction:

- 0H-) HEN Fe(CN) K 0.02 mole (288 g) S-amino 2-chloropheno1 is dissolved together with 0.02 mole (2.85 g) chloroparaphenylene diamine in 500 cc water to which cc ammonia 22Be' has been added. Into the resulting mixture there is introduced, little by little, with agitation, 0.04 mole (13.20 g) potassium ferricyanide dis solved in 300 cc water. 5.80 g of the above indoaniline in crystalline form which melts at are recovered by filtering on a suction filter the reaction mixture.

CH CH 3 3 CH H3 CH3 CH3 an 0H- ]{,N N o 2 m2 Fe(CN) K 2 g CH CH CH3 3 2 CH3 3 NH? To 200 cc water to which there has been added 10 cc 60 Molecuiar Wight Calculated for CuHoNaClzO ammonia 22 Be, there is added, with agitation, 0.02 mole (4.74 g) 1,4 diamino durene dichlorhydrate, and a solution of 0.02 mole (2.46 g) S-arnino 2-methy1 phenol in 200 cc water containing 75 cc ammonia 22Be'. into this mixture there is then introduced, little by little, 0.04 mole (13.16 g) potassium ferricyanide dissolved in cc water. After two hours of agitation, 3.4 g of the above indoaniline is recovered by filtering 282 Molecular weight found by potentiometn'c determination effected with perchloric acid in acetic medium 281 Calcuiated for Analysis C,,H,N Cl,0 Found C 51.06 50.95 H 3.19 3.35 N 14.39 14.95 14.96

EXAMPLE I 1 ing the reaction mixture on a suction filter. After washing with water and recrystallization from a pyridine and water mixture, the resulting indoaniline exhibited a melting point of 199.

N-[(4'-amino 2'-methoxy) phenyl] 6-methyl 3- methylamino benzoquinone imine is prepared in accordance with the following reaction:

OCH N'HCH 0.05 mole (10.55g) methoxyparaphenylenediamine Calculated for dichlorhydrate 1S dissolved m 250 cc water and the pH Analysis c onq Found is adjusted to 8 by addition thereto of ammonia. This C 64 43 6398 solution is immediately added to 0.025 mole (3.5 g) H ,03

2-methyl S-methylamino phenol previously dissolved in 250 cc water and to which 75 cc ammonia 22Be' has been added. 300 cc hydrogen peroxide is added to the mixture to 20 volumes and then the mixture is allowed EXAMPLE 13 to stand at room temperature for 4 hours. By filtering the mixture, there is then obtained 4.17 g of the above 25 indoaniline in crystalline form, which, after washing N-[4'-amino 3"methyl)phenyl] 3-amino-2,6- with water and recrystallization from a mixture of acedimethyl benzoquinone imine is prepared in accortone and water, exhibits a melting point of 125. dance with the following reaction:

H CH CH C 3 H N NH H)H N N Fe CN K; 3 CH CH Calculated for 0.025 mole (4.87 g) paratoluylenediamine dichlorhy- Analysis C ,H,,N,O, Found drate 1S dlssolved in 200 cc water and the pH of the C A2 66] solution is adjusted to 8 by addition thereto of ammo- H 6.27 6.39 nia. This solution is immediately added to 0.02 mole N% 15.49 15.41 15.42

(2.74 g) 3-amino-2,6 dimethyl phenol previously dis solved in 200 cc water and to which 60 cc ammonia EXAMPLE 12 22Be' has been added. To this resulting mixture there is added, little by little, in the course of 20 minutes,

N-[(4'- i 3'- 1h h 3- b l with agitation, 0.05 mole (16.45 g) potassium ferricyathylamino G-methyl benzoquinone imine is prepared in nide dissolved in 250 cc water.

accordance with the following reaction: 3.4 g of the above indoaniline is recovered by filter- CH3 CH3 H N NH2 -OH) H2N N o CH3 H3 0.1 mole (19.5 g) paratoluylenediamme dlchlorhying the reaction mixture on a suction filter. The ind rate is dissol ed in 00 CC wa The P Of this doaniline product is then washed with water and after adlusted 8 y addmon thereto 0f ammonlarecrystallization from a dirnethyl formamide and water This solution is immediately added to mole 8) mixture, the product exhibits a melting point of 190. N-S-carbamylmethylamino Z-methyl phenol previously dissolved in 400 cc water. cc ammonia 22Be' and Anal is i f ag Found 500 cc hydrogen peroxide to make 20 volumes are then y added to this mixture which is allowed to stand for 5 5; 2-22 72.2:

hours at ambient temperature. 7.40 g of the above N% 16:47 1M6 16.19

indoaniline in crystalline form are recovered by filterl3 EXAMPLE 14 N-[(4'-amino 2'-methoxy)phenyl] 3-amino 2,6- dimethyl benzoquinone amine is prepared in accordance with the following reaction:

14 g) potassium ferricyanide. When the addition is completed, 5 g of the above indoaniline is recovered by filtering the reaction mixture on a suction filter. The indoaniline is then washed with water and after recrys- N112 2 0011 CH3 CH H2NNH2 H W HEN N C 0.01 mole (2.11 g) methoxyparaphenylenediamine dichlorhydrate is dissolved in 100 cc water and the pH thereof is adjusted to 8 by addition of ammonia. This solution is immediately added to 0.01 mole (1.37 g) 3-amino 2,6-dimethyl phenol, preliminarily dissolved in 100 cc water. There is added to this resulting mixture cc ammonia 22Be' and 130 cc hydrogen peroxide to make 20 volumes, and the mixture is allowed to stand at room temperature for four hours. On filtering 25 the reaction mixture on a suction filter there is obtained 1.8 g of the above indoaniline in crystalline form which melts at 217. After a recrystallization from a mixture of dimethylformamide and water, the said indoaniline exhibited the same melting point.

OCH

HZNAQNI Calculated for Analysis C H N,O, Found C 66.42 66.29 H I: 6.27 6.36 N 15.49 15.50

EXAMPLE l5 N-[4'-amino 3 chloro )phenyl] 3-amino 2,6-dimethyl benzoquinone imine is prepared in accordance with the following reaction:

H N I 2 m2 Fe(CN) K tallization from a mixture of dimethylformamide and water, the product exhibited a melting point of 196.

Calculated for Analysis C H O N,Cl Found C 60.98 60.51 60.61 H 5.08 5.17 5.30 N 15.24 15.17 14.95

EXAMPLE 16 N-[(4'-amino 2'-methoxy 5'-methyl) phenyl] 3- amino-2,6-dimethyl benzoquinone imine is prepared in 3 accordance with the following reaction:

0.2 mole (4.5 g) 2-methoxy-5-methy1 paraphenylenediamine dichlorhydrate is dissolved in 200 cc water and the pH thereof is adjusted to 8 by the addition thereto of ammonia. This solution is immediately added to 0.02 mole (2.74 g) 3-amino-2,6-dimethyl phenol, previously dissolved in 200 cc water. To the resulting mixture there is added cc ammonia 22Be' and 260 cc hydrogen peroxide to make 20 volumes. The mixture is Z Cl CH e 0.02 mole (2.74 g) 3-amino 2,6-dimethyl phenol and allowed to stand at room temperature for four hours.

0.02 mole (2.85 g) chloroparaphenylenediamine are dissolved in 200 cc water to which there has been added 50 cc ammonia 22Be. Little by little, there is added to this mixture, with agitation, 0.04 mole (13.16

On filtering the reaction mixture on a suction filter, there is obtained 3.1 g of said indoaniline in crystalline form, which after recrystallization from a mixture of pyridine and water, exhibits a melting point of a N OH N N o 2 NH? Fe(CN) K H2 Calculated for solved in two liters of iced water to which one liter Analysis C,,H,.N,O, Found ammonia 22Be' has been added. Into the resulting C 67.36 6634 6645 mixture there is introduced, little by little, in the course H 6.66 6.71 6.75 5 of one half hour and with agitation, a solution of 0.8 N 14-73 14-80 mole (262 g) potassium ferricyanide in 1300 cc water. On filtering the reaction mixture on a suction filter 50 EXAMPLE 7 g of said indoaniline in crystalline form is recovered.

This product, after washing with water and then with y l p y to acetone and recrystallization from a dimethylformamdimethy] benzoqulnone imine is P p in QCCOF- ide and water mixture, exhibited a melting point of dance with the following reaction: 141

CH CH CH CH CH CH 2 NEE OHWHZ N CH CH CH CH 3 3 3 3 CH NR CH NR A first solution is prepared by dissolving 0.02 mole (4.74 g) l,4-diaminodurene dichlorhydrate in 200 cc 25 Anakysis ggfii'ffjgf' Found of a 0.2 N NaOH solution. A second solution is prepared by dissolving 0.02 mole (2.74 g) 3-diamino-2,6- 5?; 22-, 2:38 2: 5 dimethylphenol in 200 cc of a 0.2 N NaOH solution. N l5.6l 15.64 15.57

The two solutions are mixed and there is slowly added thereto, with agitation, 0.02 mole (5.4 g) potassium persulfate in solution in 200 cc water. When the addi- EXAMPLE '9 tion 15 completed, the mixture lS allowed to stand for one hour at room temperature. On filtering the reaction mixture on a suction filter 3.7 g of said indoaniline is recovered. After recrystallization from a dimethyL yy p y formamide and water mixture, the said indoaniline acetylamino benzoquinone imine is prepared in accore hibir d a melting oi t of 210, dance with the following reaction:

CH CH H N OH --)H N N O 2 2 Fe-(CN) K 2 OCH COCH OCH 1 ICOCH 3 NH 3 Calculamd f To a solution of 0.02 mole (4.5 g) Z-methoxy-S- Analysis C H N O Found methyl paraphenylene diamine dichlorhydrate in 200 N l4 14 1337 1339 cc water there is added 10 cc ammonia 22Be and then 0.02 mole (3.02 g) 3-acetylamino phenol, previously dissolved in 200 cc iced water to which 60 cc ammonia EXAMPLE 18 22Be' has been added. Into the resulting mixture there N-[ (4'-amino-3' methyl) phenyl] 3-acetylamino benis introduced, little by little, with agitation, a solution of zoquinone is prepared in accordance with the following mole g) Potassium fe icyanide in 250 cc reaction: water. After one hour of agitation, the above indoani- NHCOCH CH COCH 0.4 mole (78 g) paratoluylenediamine dichlorhydrate line in an ammount of4.4 g is recovered by filtering the is dissolved in 500 cc water to which 50 cc ammonia reaction mixture on a suction filter. After recrystalliza- 22Be has been added. This solution is mixed with 0.4 tion i a at and idin i t r th aid indoanimole (60.4 g) 3-acetylamino phenol, previously disli hibi d a l i i t f 255,

I Calculated for Analysis C l-l O N Found C 64.21 64.27 H 5.68 5.87 N 14.04 13.90 13.96

EXAMPLE 20 N-[(4'-amino) phenyl] -acetylamino-2-methy1 benzoquinone imine is prepared in accordance with the following reaction:

NHCOCH H N NH OH- )H N ii 0 OCH filter. After washing with acetone and recrystallization from a dimethylformamide and water mixture, this indoaniline exhibited a melting point of 105.

5-acety1amino-2-methy1 phenol, previously dissolved in 200 cc water to which 60 cc ammonia 22Be' has been added. Into the resulting mixture there is introduced, little by little, with agitation, a solution of 0.04 mole (13.1 g) potassium ferricyanide in 200 cc water. After an hour of agitation, the reaction mixture is filtered off and there is recovered 3.80 g of said indoaniline in crystalline form. After recrystallization from a dimethylformamide and water mixture, the said indoaniline exhibited a melting point of 140.

NHCOCH Calculated for Analysis c H mo, Found C 67.84 66.37 66.50 H 6.00 6H 6.16

EXAMPLE 22 N[(4-amino-2"methoxy) phenyl] 3-acetylamino-6- methyl benzoquinone imine is prepared in accordance with the following reaction:

NHCOCH3 001-1 3 A first solution is prepared by dissolving 0.02 mole (4.22 g) 2,5-diamino anisole dichlorhydrate in 200 cc HCOCH of a 0.2 N NaOH solution. A second solution is prepared by dissolving 0.02 mole (3.3 g) 5acety1amino-2- methyl phenol in 200 cc ofa 0.2 N NaOH solution. The two solutions are mixed and there is then slowly added, with agitation, 0.02 mole (5.4 g) potassium persulfate, previously dissolved in 250 cc water. When the addition is completed, the reaction mixture is filtered off and 3.1 g of said indoaniline is recovered, which, after recrystallization from a mixture of dimethylformamide methyl benzoquinone imine is prepared in accordance and wamr' exhibited a melting POint of 2150- with the following reaction:

mine dichlorhydrate in 200 cc water, there is added cc ammonia 22Be' and then 0.02 mole (3.30 g) H NHCOCH3 Calculated for Analysis C H Q-fl l Found C 7r 64.21 64.45 64.16 H :1 5.68 5.90 5.82

cc water, there is added l cc ammonia 22Be' and EXAMPLE 23 then 0.02 mole (3.30 g) S-acetylaminoQ-methyl phe- N-[(4'-amino-3'-chloro) phenyl] 3-acetylamino-6- n01, previously dissolved in 200 cc iced water to which methyl benzoquinone imine is prepared in accordance 60 cc ammonia 22Be' has been added. Into the resultwith the following reaction: 5 ing mixture there is introduced, little by little, with CH CH H N NR H -9 H N N 0 F CN K 3 Cl NhCOCH3 Cl NHCOCH3 0.02 mole (3.30 g) S-acetylarnino-Z-methyl phenol agitation, a solution of 0.04 mole (13.! g) potassium and 0.02 mole (2.85 g) chloroparaphenylene diamine ferricyanide in 250 cc water. After 1 hour of agitation, are dissolved in 500 cc water to which there has been the C n mixture i filtered Off and 5.4 g of said added 70 cc ammonia 22Be. Into the resulting mixindoaniline is recovered which, after recrystallization ture, there is introduced, little by little, with agitation, from ethyl acetate, exhibited a melting point of 220". 0.04 mole (13.16 g) potassium ferricyanide in solution in 300 cc water. On filtering the reaction mixture on a suction filter, 3.8 g of said indoaniline in crystalline Molecularwelghtcalculmcdf'C}1H1'N?0' 313 Molecular weight found by potentiometnc form is recovered which, after recrystallization from a d m i ti fi d with perchlofic mixture of pyridine and water, exhibited a melting 25 acid in acetic medium 3|6 point of 215".

Molecular weight calculated for C ,H, N ,O,Cl: 303.5 Calculated for so an acetic medium 292 N 1340 1333 1342 C l ulated for Analysis C: l -l N,O,Cl Found EXAMPLE 25 (3% 5348 N-[(4'-amino tetramethyl) phenyl] 3-acetylamino-6- 2 2 gig; 3.69 4.67 13 m ethyl benzoquinone imine is prepared in accordance with the following reaction:

40 CH3 CH CH CH CH CH a N NR OH H N N 0 2 Fe(CN) K CH NHCOCH CH NHCOCH CH 3 3 CH 3 3 EXAMPLE 24 To a solution of 0.02 mole (4.74 g) 1,4-diaminodurene dichlorhydrate in 200 cc water, there is added 10 cc ammonia 22Be' and then 0.02 mole (3.30 g) 5- acetylamino-Z-rnethyl phenol, previously dissolved in N-[4'-amino-2'-methoxy-5-methyl) phenyl] 3- acetylamino-fi-methyl benzoquinone imine is prepared in accordance with the following reaction:

NHCOCH NHCOCH To a solution of 0.02 mole (4.5 g) 2-methoxy-5- 200 cc water to which cc ammonia 22Be' had been methyl paraphenylene diamine dichlorhydrate in 200 added. Into the resulting mixture there is introduced,

3,929,403 21 22 little by little, with agitation, a solution of 0.04 mole EXAMPLE 27 (13.1 g) potassium ferricyanide in 200 cc water. After an hour of agitation, the reaction mixture is filtered off and 3.5 g of said indoaniline in crystalline form is re- N-[(4'-amino)phenyl] 3-acetylamino-2,6-dimethyl covered, which after recrystallization from a mixture of benzoquinone imine is prepared in accordance with the pyridine and water exhibited a melting point of 270". following reaction:

CH CH H N NH 0H H N N O CH H CH CONH 3 CH coma 3 3 v 3 Molecular weight calculated for c u n o, 325 A first Solution is p p y qissolving mole Molecular weight found by potentiometric (l0.9 g) paraphenylene diamme dichlorhydrate m 600 determmam" Qffecled E l cc of a 0.2 N NaOH solution. A second solution is butylketone, using perchlortc acid 337 prepared by dissolving 0.06 mole (10.8 g) 3- acetylamino-2,6-dimethyl phenol in 600 cc of a 0.2 N NaOH solution. The two solutions are mixed and there is then slowly added, with agitation, 0.06 mole (l6.2 g)

Calculated for potassium persulfate in solution in 600 cc water. When Analysis C,.H,,N,0, Found the addition is completed, the reaction mixture is al- C 7015 6937 69M lowed to stand at room temperature for one hour. "lthe H 7.07 7.19 7.04 reaction mixture is then filtered off and the above In- N 12-92 1237 doaniline is recovered, which after recrystallization from a mixture of dimethylformamide and water exhibited a melting point of 220.

Calculated for EXAMPLE 26 Anawsis CMHHON: Found N-[(4'-amino-3'methyl) phenyl] 2-acetylamino ben- C 6734 67.64 zoquinone imine is prepared in accordance with the L 61)! 6.24 following reaction: [498 H N NH Ol-l H N N O CH CH 3 NHCO 3 CH NHCOCH A first solution is prepared by dissolving 0.02 mole EXAMPLE 28 (3.90 g) paratoluylenediamine dichlorhydrate in 200 cc of a 0.2 N NaOH solution. A second solution is P p y dissolving mole g) The indoaniline of Example 16, i.e. N-[(4'-amino acetylamino phenol in 200 cc of a 0.2 N NaOH solugzmethoxy 5' methy|)pheny|] 3- i -2 6-di h ti n- Th tW Solutions are mixed and there is benzoquinone imine is prepared in accordance with the slowly added, with agitation, 0.02 mole (5.4 g) potasf llo i g two stage reaction;

sium persulfate dissolved in 250 cc water. When the addition is completed, the reaction mixture is allowed to stand for one hour at ambient temperature. On filtering the reaction mixture on a suction filter, 4.5 g of said indoaniline is recovered, which after recrystallization from a mixture of dimethylformamide and water, ex- 3 hibited a melting point of 1 10.

1st Stage:

2 2 Calculated for Ag 0 Analysis C,,H N,0, Found N l5.6l 15.77 l5.83 OCH 23 24 2nd Stage:

CH3 CH3 H3 as as H ---+H2N It? OCH cs OCH ca lst Stage: EXAMPLE 29 2-methyl-5-methoxy benzoquinone diimine is prepared as follows:

0.056 mole (8.56 g) Z-methyl S-methoxy paraphenylenediamine is introduced into 850 cc isopropyl anhydrous ether to which there has been added 0.085 mole (19.7 g) silver oxide and 55 g anhydrous sodium sulfate. The mixture is agitated for two hours, maintaining the temperature thereof between and After 3 cooling, the sodium sulfate and the silver are separated from the reaction mixture by filtration, and the result- 2 2 3 EN ing filtrate is evaporated to dryness under vacuum. The Ag 0 dry residue, after recrystallization from a mixture of 25 2 OCH OCH 15 The indoaniline of Example 19, Le. N[(4amino-2- methoxy-S-methyl)phenyl] 3-acetylamino benzoquinone imine is prepared in accordance with the following two stage reaction: 1st Stage:

benzene-hexane, furnishes 5.8 g Z-methoxyS-methyl benzoquinone diimine, which has a melting point of 3 2nd Stage:

CH CH 3 3 I'lli- NH OHQH N-QN{}Q 001-1 NHCOCH CH N'HCOCH 40 Calculated for 1st Stage I Analysis C,H ,N,0 Found 2-methyl-S-methoxy-benzoqumone imine IS prepared C 6400 64,17 essentially in the same manner outlined in the first H 6:66 6.74 stage of Example 28. 2nd Stage: 18-58 The desired indoaniline, N-[(4'-amino-2-methoxy- 5'-methyl)phenyl] 3-acetylamino benzoquinone imine is prepared as follows:

0.003 mole (0.4 g) 3-acetylamino phenol is dissolved 2nd slage! in 70 cc water to which 10 cc ammonia 22Be' has been The desired indoaniline. -l( Y' added. To this solution there is added 0.0035 mole y )p y l 3-amin0 2,6-dimethyl q 0.52 g) 2-methyl-5-methoxy-benzoquinonediimine imine is P p as follows: from the first stage in solution in cc water. The mole (1-50 9 y s'methoxy mixture is agitated for half an hour. The reaction mixnone diimlne P p in the first Stage of macho" ture is filtered off and 0.62 g. of the above indoaniline is dissolved in 100 cc anhydrous ether. 0.0l mole (1.37 g) 3-amino-2,6-dimethyl phenol in solution in 50 cc anhydrous ether is then added to the same. The resulting reaction mixture is allowed to stand for four hours is recovered which exhibits a melting point of 252.

at room temperature, and the solvent is driven off Molecular weight calculated for CQHl 108m 299 under vacuum, the residue being crystallized in a mix- Molecular weight found by potentiometric ture of pyridine and water. The above indoaniline thus determmatm 290 etic medium obtained exhibits a melting point of 145. ac

EXAMPLE 30 Molecular weight calculated for C,.H N,O, 285 h mdoam'hne of Example 8! fl ammo 3 Molecular weight found by potentiometric 5 -dlmethyl-2 rnethoxy) phenyl] 3-ammo 6-rnethyl sing Pew"loric acid in benzoquinone imine is prepared in accordance w1th the methylisobutylacetone 277 following two stage reaction:

1st Stage:

CH3 CH '1'! N N -7 HN NH 2 H2 Ag F OCH OCH it 3 3 I 3 CH 2nd Stage:

C CH3 CH3 3 RN? @OHQ HEN N OCH OCH NH 3 3 2 CH3 CH 1st Stage:

3,5-dimethyl-2methoxy benzoquinone diimine is prepared as follows:

0.037 mole (6.10 g) 2-methoxy-3,5-dimethyl paraphenylene diamine is introduced into 350 cc anhydrous ether to which there has been added 0.055 mole 12.7 g) silver oxide and 35 g anhydrous sodium sulfate. The mixture is heated to reflux for two hours with maintenance of good agitation. After cooling, the sodium sulfate and the silver are filtered out and the filtrate is evaporated to dryness under vacuum. The dry residue, which is the above diimine, after recrystallization in cyclohexane exhibits a melting point of 47.

The desired indoaniline N-[(4'-amino-3',5'-dirnethyl-2-methoxy)phenyl] 3-amino-6-methyl benzoquinone imine is prepared as follows:

0.0028 mole (0.34 g) S-amino-Z-methyl phenol is dissolved in 70 cc water to which 10 cc ammonia 22Be has been added. To this solution there is added 0.036 mole (0.59 g) 3,5-dimethyl-2-methoxy benzoquinone diimine from the first stage in 60 cc water. The mixture is agitated for 30 minutes. The reaction mixture is then filtered off and 0.55 g of the above indoaniline is recovered, which exhibits a melting point of 205.

Molecular weight calculated for C .H ,N,O, 285 Molecular weight found by potentiometric determination using perchloric acid in methylisobutylacetone 286 EXAMPLE 31 N-[(4'amino 2',5'dimethoxy) phenyl] 3-amino-6- methyl benzoquinone imine is prepared in accordance with the following two stage reaction: 1st Stage:

cells N NH 5HN H2 2 A95 0 Q H OCH 2nd Stage:

OH-7 11 N= =o CH3 OCH H3 1st Stage:

2,5-dimethoxy benzoquinone diimine is prepared as follows:

0.06 mole (10 g) 2,5-dimethoxy paraphenylene diamine is introduced into a liter of anhydrous isopropyl ether. 21 g silver oxide and 48 g anhydrous sodium sulfate are then added to the same. The resulting mixture is heated at reflux for 6 hours, while maintaining good agitation. After cooling the reaction mixture the sodium sulfate and the silver are filtered out and the filtrate is evaporated to dryness under vacuum. The dry 0 residue which is the above diimine, after recrystallization from a benzene-petroleum ether mixture, yields pure 2,5-dimethoxy benzoquinone diimine having a melting point of 184.

Calculated for Analysis C,H,.,N O, Found C it: 57.80 57.79 57.60 H I: 6.03 6.12 6.06 N 16.87 16.80 16.85

EXAMPLE 32 The following dye composition, in accordance with the present invention is prepared as follows:

The indoaniline of Example 2 0. l5 Water in sufl'icient quantity to make up l00 g Ammonia 22Be' in sufficient quantity for pH The dye composition is applied to 100 percent white hair for minutes and yields after rinsing and shampooing a blue lavender tint.

EXAMPLE 33 The following dye composition, also in accordance with this invention, is prepared as follows:

The indoaniline of Example 5 0.2 g Butyl glycol S g Laurie alcohol oxyethylenated with 10.5

mole ethylene oxide 5 g Water in sufficient quantity to make l00 g This dye composition, which has a pH of 7, is applied to 90 percent grey hair. After a waiting time of 20 minutes, followed by a rinse and shampoo, a purplish violet coloration is obtained.

EXAMPLE 34 Another dye composition of the present invention is prepared as follows:

The indoaniline of Example 7 0.l g Ammonium lauryl sulfate with 20% lauric alcohol 20 g Ethylenediamine tetraacetic acid 0.2 g Ammonia 22Be' l cc Water in sufficient quantity to make l00 g This dye composition, which as a pH of 1 l, is applied for 20 minutes to platinum hair. After rinsing and shampooing a rosewood coloration is imparted to the hair.

EXAMPLE 35 Yet another dye composition of the present invention is formulated as follows:

The indoanlline of Example ll 0.05 g Ammonium lauryl sulfate with 20% lauric alcohol 20 g Ethylenediamine tetraacetic acid 0.2 g Ammonia ZZ'Be' 1 cc Water in sufficient quantity to make up 100 g This dye composition, which has a pH of ll, is applied for 30 minutes to 100 percent white hair. After rinsing and shampooing, a mauve coloration is obtained.

EXAMPLE 36 The following dye composition is prepared:

The indoaniline of Example 13 0 Butylglycol Lauric alcohol oxyethylenated with 10.5 moles ethylene oxide Water in sufficient quantity to make up This solution, which has a pH of 7, is applied to 100 percent white hair for 20 minutes. After rinsing and shampooing, a pink coloration is imparted to the hair.

EXAMPLE 37 Still another dye composition in accordance with the present invention is prepared as follows:

The indoaniline of Example 20 0.1 g Butylglycol 5 g Laurie alcohol oxyethylenated with 10.5 moles ethylene oxide 5 g Water in sufficient quantity to make up I00 g This dye composition, which has a pH of 7, is applied for 20 minutes to 100 percent white hair. After rinsing and shampooing, a mauve tint is imparted to the hair.

EXAMPLE 38 The following dye composition comprises:

The indoaniline of Example 26 0.1 3 Water in sufficient quantity to make up 100% Ammonia 22Be' in sufficient quantity for pH grey dye composition is applied to percent gray hair for 20 minutes and after rinsing and shampooing a bluegrey coloration is imparted to the hair.

EXAMPLE 39 A hair set lotion is formulated in accordance with the present invention:

The indoaniline of Example 5 0.1 g Co polymer of crotonic acid and vinyl acetate 2 g 96 titer ethanol in sufficient quantity to make 50 g Water in sufficient quantity to make up I00 g This hair set lotion is applied to I00 percent white hair and imparts a purple sheen.

EXAMPLE 40 The following dye composition comprises:

The indoaniline of Example 3| 0.2 g 96' titer ethanol 20 3 Water in sufficient amount to make up 100 Ammonia 22'Be' in sufficient quantity for pH 9.;

This dye composition is applied for 20 minutes to percent white hair. After rinsing and shampooing an ashen-grey coloration is imparted to the hair.

Equally favorable dye compositions and hair set lotions are prepared employing the other indoanilines disclosed hereinbefore.

EXAMPLE 41 Preparation of N-[(amino-4' methoxy-2') phenyl] dimethyl-2,6 benzoquinone imine, having the formula N- N H2 0 Initially 0.15 mole (31.65 g) of the dichlorohydrate of methoxyparaphenylene diamine is dissolved in 900 cc of a 0.33 N NaOH solution. Separately, 0.15 mole (18.3 g) of 2,6-xylenol is dissolved in 450 cc of a 0.66 N NaOH solution. The two solutions are then mixed, to 2 which mixture there is slowly added with agitation, 34.2 g of ammonium persulfate in 200 cc of water. Thereafter, the reaction mixture is allowed to stand for 10 minutes at ambient temperature. Then, by filtering, there is separated 17.5 g of the above indoaniline, which, after washing with water and with acetone and then drying under vacuum, has a melting point of 182C. and is chromatographically pure.

Molecular weight calculated for C, .,H ,N,O 256.

Molecular weight found by potentiometric determination effected in methylisobutylketone using perchloric acid 261.

phenyl] 2,6-dimethyl benzoquinone imine having the formula To a solution cooled to 0C. and containing 2.28 g of ammonium persulfate in 20 cc water, cc of acetone and 10 cc ammonia (22 Be), there is added 0.01 mole (2.41 g) of the dihydrochloride of 2.5 dimethoxy paraphenylene diamine dissolved in 25 cc of water. This mixture is then immediately added to a solution, which has been cooled in ice, containing 0.01 mole of 2,6-xylenol (1.22 g) in 50 cc of water, 20 cc of ammonia (22Be) and 5 cc of acetone. The resulting reaction mixture immediately turns blue-green. There is then added 175 cc of water and, by filtering there is separated 1.2 g of the above indoaniline, which after washing with water and drying under a vacuum, is chromatographically pure and melts at 170C.

Molecular weight calculated for C H N O 286.

Molecular weight found by potentiometric determination effected with m'ethylisobutylketone in perchloric acid 294.

Preparation of N-[(4-arnino 2'-methoxy 5'-methyl) phenyl] Z-methyl S-amino benzoquinone imine, having the formula OCH There is dissolved 0.1 mole (12.3 g) of 2-methyl, S-amino phenol in 350 cc of water to which has been added cc of ammonia (22Be). To this solution there is added simultaneously through two dropping funnels, a solution of 0.1 mole (22.5 g) of the dichlorohydrate of 2-methoxy S-methyl paraphenylenediamine in 100 cc of water through one of the funnels, and a solution of 0.1 mole (22.8 g) of ammonium persulfate in 50 cc of water through the other, while the reaction mixture is cooled in ice. Thereafter, the reaction mixture is allowed to stand 15 minutes at ambient temperature and there is recovered by filtering 8.8 g of the above indoaniline. After recrystallization in a mixture of pyridine and water and after drying under vacuum, the resulting product exhibited a melting point of 158C.

Analysis Calculated for Found CIBHHHSODOS H20 C 64.29 64.64 64.57 H 6.42 6.66 6.57 N 15.00 15.00 14.94

EXAMPLE 44 Preparation of N-[(4'-amino)phenyl]3-amino 2,6- dimethyl benzoquinone imine having the formula NH CH There is dissolved 0.1 mole (13.7 g) of 2,6-dimethyl 3-amino phenol in one liter of water to which has been added 400 cc of ammonia. To the resulting solution there is added 0.1 mole (10.8 g) of paraphenylene diamine in one liter of water. To this resulting mixture there is then added 1300 cc of H 0, (20 volumes). The reaction mixture is then allowed to stand for 5 hours at ambient temperature after which 10.5 g of the above indoaniline in crystalline form are separated by filtering. After washing with water, and recrystallization from a mixture of pyridine and water, followed by drying under vacuum, the resulting product exhibited a melting point of 188C.

Preparation of N-[(4'-amino 2',5'dimethoxy)phenyl] Z-methyl S-acetylamino benzoquinone imine having the formula OCH NHCOCH To a solution cooled to 0C. and containing 2.28 g of ammonium persulfate in 20 cc of water, 50 cc of acetone and cc of ammonia (22Be) there is added 0.01 mole (2.41 g) of the dichlorohydrate of 2,5-dimethoxy paraphenylene diamine dissolved in 25 cc of water. There is then immediately added to the mixture thus obtained, a solution, cooled in ice, of 0.01 mole (1.65 g) of 2-methyl S-acetylamino phenol in 20 cc of 0.5 N NaOH solution. The above indoaniline precipitates immediately. The precipitate is filtered and then washed with water and with acetone. The washed precipitate is then dried under vacuum. The resulting indoaniline thus prepared is chromatographically pure and exhibits a melting point of 235C.

Preparation of N-[(4'-amino, 3'-methyl) phenyl] 3-acetylamino, 2,6-dimethyl benzoquinone imine having the formula 32 CH 011 001111 CH To a solution containing 0.02 mole (3.58 g) of 2,6- dimethyl 3-acety1amino phenol in 48 cc of acetone there is added 0.02 mole (3.90 g) of the dichlorohydrate of paratoluene diamine in 35 cc of water to which has been added 13 cc of ammonia (22Be). Into this resulting mixture there is added, little by little, with agitation, 0.03 mole (6.84 g) of ammonium persulfate dissolved in 15 cc of water. The resulting reaction mixture is permitted to stand for 15 minutes at ambient temperature. By filtering 2.94 g of the above indoani line are recovered, which after washing with water and with acetone, followed by recrystallization from a mixture of pyridine and water, exhibited a melting point of 185C.

Preparation of N-[(4'-amino Z-methoxy 5-methyl) phenyl] 3-acetylamino 2,6-dimethyl benzoquinone imine having the formula CH CH COHN 0 3 3 CH 0.03 mole (5.3-, g) of 2,6-dimethyl 3-acetylamino phenol is dissolved in 200 cc of water to which has been added cc of ammonia (22Be). To this solution there is simultaneously added through two dropping funnels, a solution of 0.03 mole (6.75 g) of the dichlorohydrate of Z-methoxy S-methyl paraphenylenediamine through one funnel and a solution of 0.06 mole (19.75 g) of potassium ferricyanide in 200 cc of water through the other funnel, the reaction mixture being maintained at a temperature not greater than about 10C. After the addition of the two above solutions is completed, the reaction mixture is permitted to stand for about 20 minutes at about 10C. After filtering 4.40 g of the above indoaniline are recovered, which after recrystallization from a mixture of dimethylformamide and water, exhibited a melting point of 236C.

Preparation of N-[(4'-amino 2'-methoxy)phenyl 3-acetylamino benzoquinone imine having the formula NHCO CH Initially, there is dissolved 0.01 mole (2.1 1 g) of the dichlorohydrate of methoxy paraphenylenediamine in 50 cc of water. Separately, there is dissolved 0.01 mole (1.51 g) of m-acetylaminophenol in 100 cc of water to which has been added 30 cc of ammonia (22Be). The above two solutions are then mixed together and to this resulting mixture there is slowly added, with agitation, 0.02 mole (6.58 g) of potassium ferricyanide in 50 cc of water while maintaining the reaction temperature between 5 and C. There is then recovered from the reaction mixture, by filtering, 1.42 g of the above indoaniline. After washing the same with water and after recrystallization in a mixture of pyridine and water, the product was chromatographically pure and exhibited a Molecular weight calculated for C H N O 285.

Molecular weight found by potentiometric determination effected in acetic acid with perchloric acid 289.

EXAMPLE 49 The following dye solution is prepared:

Compound of example 42 0.2 g Ethylalcohol (96) 50 g Ammonia (22Be') q.s.p. pH 10 Water q.s.p. 100 g This solution is applied to bleached hair at ambient temperature. After 20 minutes, the hair is rinsed and shampooed and there is obtained a very clear jade green coloration.

EXAMPLE 50 The following dye solution is prepared:

The compound of Example 44 0.05 g Copolymer of 10% crotonic acid-90% vinyl acetate (M.W. 45000-50000) 2 Ethylalcohol (96) q.s.p. 5 Triethanolamine q.s.p. pH 7 Water q.s.p. loo 8 This solution is applied as a hair setting lotion on 100 percent white hair and imparts thereto a pearlescent rose coloration lightly tinted mauve.

EXAMPLE 51 The following solution is prepared:

The compound of Example 47 0.05 g Copolymer of crotonic acid-vinyl acetate (as in Example 50) 2 g Ethyl alcohol (96) q.s.p. 50 Triethanolamine q.s.p. pH 7 Water q.s.p. 100 g This solution is applied as a hair setting lotion to bleached hair and imparts thereto a silvery pastel blue coloration.

EXAMPLE 52 The following solution is prepared:

This solution is applied as a hair setting lotion to bleached hair and imparts thereto a very luminous deep blue coloration.

EXAMPLE 53 The following dye solution is prepared:

The compound of Example 44 0.5 g Ethyl alcohol (96) 25 g Water .s. 100 g I P- Ammonia (22Be') q.s.p. pH 10 This solution is applied to bleached hair at ambient temperature and after 20 minutes the hair is rinsed and shampooed. A bright crimson rose coloration is obtained.

EXAMPLE 54 The following dye solution is prepared:

The compound of Example 41 0.3 g Ethyl alcohol (96) 25 g Water 100 g q s.p. Ammonia (22Be') q.s.p. pH 10 This solution is applied to percent naturally white hair at ambient temperature and after 20 minutes the hair is rinsed and shampooed. A blue gray coloration is obtained.

EXAMPLE 55 The following dye solution is prepared:

The compound of Example 42 0.1 g Copolymer of crotonic acid-vinyl acetate (as in Example 50) 2 g Ethyl alcohol (96) q.s.p. 50 Water q.s.p. 100 g Triethanolamine q.s.p. pH 7 This solution is applied as a hair setting lotion to bleached hair and imparts thereto a deep turquoise blue coloration.

EXAMPLE 56 The following hair dye solution is prepared:

Compound of Example 45 0.05 g Copolymer of crotonic acid-vinyl acetate (Example 50) 2 G Ethyl alcohol (96) q.s.p. 50'' Water q.s.p. 100 g Triethanolamine q.s.p. pH 7 This solution is applied as a hair setting lotion on bleached hair and imparts thereto a clear and pearlescent turquoise blue coloration.

This solution is applied as a hair setting lotion on bleached hair and imparts thereto a light pearlescent mauve coloration.

EXAMPLE 58 30 The following solution 18 prepared:

The compound of Example 44 0.4 g Ethyl alcohol (96") g Water q.s.p. 100 g 3 pH 7 5 This solution is applied at C. to 95 percent natural white hair. After 20 minutes the hair is rinsed and shampooed and a violet coloration is obtained.

EXAMPLE 59 The following solution is prepared:

4 Compound of Example 0.05 g 5 Copolymer of crotonic acid and vinyl acetate (as in Example 2 g Ethyl alcohol (96) q.s.p. 50 Water q.s.p. l00 g Triethanolamine q.s.p. pH 7 This solution is applied as a hair setting lotion to bleached hair and imparts thereto a Wisteria-like coloration.

EXAMPLE 55 The following solution is prepared:

Compound of Example 46 l Nitro-orthophenylenediamine 5 Copolymer of crotonic acid-vinyl acetate (as in Example 50) 2 g Ethyl alcohol (96) q.s.p. 50 Water q.s.p. Triethanolamine q.s.p. pH 7 This solution is applied as a hair setting lotion to bleached hair and imparts thereto a verdigris coloration.

EXAMPLE 61 The following solution is prepared:

Compound of Example 4i 0.025 g Nitroparaphenylenediamine 0.05 g Copolymer of crotonic acid-vinyl acetate (As in Example 50) 2 g Ethyl alcohol (96) q.s.p. 50 Water q.s.p. I00 g Triethanolamine q.s.p. pH 7 This solution is applied as a hair setting lotion on bleached hair imparting thereto an ash gray coloration which is heavily tinted mauve.

EXAMPLE 62 The following solution is prepared:

The compound of Example 44 0.1 g N'[(4'-amino 3',5-dimethyl 2'-methoxy) phenyl]2,6-dimethyl benzoquinone imine 0.05 g Copolymer of crotonic acid-vinyl acetate (as in Example 50) 2 g Ethyl alcohol (96") q.s.p. 50 Water q.s.p. g

Triethanolamine q.s.p. pH 7 This solution is applied as a hair setting lotion to bleached hair and imparts thereto a deep mauve coloration.

EXAMPLE 63 The following solution is prepared:

Compound of Example 48 DJ g Copolymer of crotonic acid and vinyl acetate (as in Example 50) 2 Ethyl alcohol (96) q.s.pi 50 Water q.s:p. 100 g Triethanolamine q.s.p. pH 7 This solution is applied as a hair setting lotion to bleached hair and imparts thereto a lavendar blue coloration with silvery glints.

EXAMPLE 64 Preparation of N-[(4'-amino)phenyl]-3-ureido benzoquinone imine, having the formula NHCONH There is dissolved 0.25 mole (38 g) of 3-ureido phenol in 800 cc of isopropyl alcohol, 800 cc of ammonia (22Be) and 2500 cc of ice water. To this solution, cooled in a mixture of ice and salt there is added, simultaneously and little by little through two dropping funnels, a solution of 0.25 mole (45.25 g) of paraphenylene diamine dihydrochloride in 400 cc of water through one of the funnels, and a solution of 0.5 mole (114 g) of ammonium persulfate in 400 cc of water through the other funnel, with agitation. At the end of this addition step, agitation is continued for 15 minutes. The reaction mixture is then filtered to recover the above benzoquinone imine which is then washed with water and dried under a vacuum, the resulting chromatographically pure indoaniline exhibiting a melting point of 265C.

Preparation of N-[(4-amino)phenyl]-2-methyl-5- ureido benzoquinone imine having the formula NHC ONH There is dissolved 0.025 mole (4.15 g) of 2-methyl5- ureido phenol in 100 cc of isopropyl alcohol to which has been added 200 cc of ice water and 100 cc of ammonia (22Be). To this solution there is added 0.025 mole (4.52 g) of paraphenylene diamine dihydrochloride and then, little by little, and with agitation, 0.05 mole (114 g) of ammonium persulfate in 40 cc of water. Agitation of the resulting mixture is continued for minutes. The reaction mixture is then filtered to recover the above benzoquinone imine which is then washed with water. After recrystallizing the above indoaniline in a mixture of dimethylformamide and water, and drying under a vacuum at ambient temperature, the product thus obtained melts with decomposition at 255C.

Calculated for Preparation of N-[(4'-amino)phenyl]-2,6-dimethyl- S-ureido benzoquinone imine, having the formula NHCONH2 There are dissolved 0.25 mole (45.0 g) of 2,6- dimethyl-S-ureido phenol and 0.25 mole (45.2 g) of paraphenylenediamine dihydrochloride in 1 liter of isopropyl alcohol to which has been added 1250 cc of ice water and 900 cc of ammonia (22Be). There is then added to this resulting solution, little by little and with agitation, 0.5 mole(l14 g) of ammonium persulfate in 500 cc of water. When this addition step is completed, agitation of the reaction mixture is continued for 15 minutes, at which time the reaction mixture is then filtered to recover the above benzoquinone imine which is washed with water and dried under a vacuum at ambient temperature. The resulting indoaniline is chromatographically pure and melts with decomposition at 253C.

Calculated For Preparation of N-[(4'-amino-2-methoxy-5'-methyl) phenyl1-3-ureido benzoquinone imine, having the formula OCH NHCONH There is dissolved 0.12 mole (18.24 g) of 3-ureido phenol in 400 cc of isopropyl alcohol, 400 cc of ammonia (22Be) and 1250 cc of ice water. To this solution, cooled in an icesalt mixture, there is added, simultaneously and little by little, through two dropping funnels, a solution of 0.12 mol (27 g) of 2-methyl-5- methoxy paraphenylene diamine dihydrochloride in 200 cc of water through one of the funnels, and a solution of 0.24 mole (55 g) of ammonium persulfate in cc of water through the other funnel, with agitation. At the end of this addition step, agitation is continued for 15 minutes. The reaction mixture is then filtered to recover the above benzoquinone imine which is then washed with water and dried under a vacuum, the resulting chromatographically pure indoaniline exhibiting a melting point of 285C.

Calculated For 

1. A HAIR DYE COMPOSITION CONSISTING ESSENTIALLY OF A SOLUTION OF AN INDOANILINE IN A SOLVENT SELECTED FROM THE GROUP CONSISTING OF WATER AND AN AQUEOUS SOLUTION OF A LOWER ALKANOL, SAID INDOANILINE HAVING THE FORMULA
 2. The dye composition of claim 1 wherein at least two of R1 to R7 are other than hydrogen and R5 and R7 are not simultaneously chlorine.
 3. The dye composition of claim 1 having a pH ranging between about 5 to about
 11. 4. The dye composition of claim 3 having a pH ranging between 7-11.
 5. The dye composition of claim 1 wherein the solvent is an aqueous solution of a lower alkanol and said composition includes a film forming resin selected from the group consisting of polyvinylpyrrolidone, copolymer of polyvinylpyrrolidone and vinyl acetate, copolymer of vinyl acetate and crotonic acid, copolymEr of vinyl acetate, crotonic acid and an acrylic or methacrylic ester, copolymer of vinyl acetate and a vinyl alkyl ether, copolymer of vinyl acetate, crotonic acid and a vinyl ester of a long carbon chain acid or an allyl or methallyl ester of a long carbon chain acid, copolymer of an ester of an unsaturated alcohol and a short carbon chain acid, an unsaturated short carbon chain acid and at least one ester of a saturated alcohol and an unsaturated short carbon chain acid and copolymer of at least one unsaturated ester and at least one unsaturated acid, said film forming resin being present in amounts of about 1-3 weight percent based on the weight of said composition.
 6. The dye composition of claim 5 wherein the lower alkanol is selected from the group consisting of ethanol and isopropanol.
 7. The dye composition of claim 5 wherein the lower alkanol is present in amounts of about 20-50 weight percent of said composition.
 8. A method for dyeing human hair comprising impregnating the hair with a dye composition according to claim 1, permitting said composition to remain in contact with said hair for a period of time ranging from about 5 to about 30 minutes, rinsing said hair with water and drying said hair.
 9. A method for setting and temporary dyeing human hair which comprises impregnating the wet hair with a dye composition according to claim 5 and then rolling up and drying the hair. 